Thermal processing and crystallization of amorphous Mg‐Ca silicates

The structural evolution of sol–gel‐produced amorphous Mg_(x)Ca_(1–x)SiO₃ silicates is investigated. Mid‐IR Fourier transform infrared spectroscopy and synchrotron X‐ray diffraction are used to confirm the amorphous nature of the as‐prepared silicates, while subsequent in situ synchrotron X‐ray powder diffraction measurements are used to study the evolution of crystalline mineral phases as a function of annealing temperature. Multiple silicate phases, including diopside, enstatite, forsterite, and SiO₂, are identified, while Rietveld (i.e., structure) refinement of the diffraction data is used to quantify phase change relationships. Investigated as possible analogs for the refractory dust grain materials likely to have been present in the early solar nebula, the likely relevance of these investigations to the observed silicate compositions of chondritic meteorites and cometary bodies and the processing of their precursor materials is discussed.     

Dust Grains in the Comae and Tails of Sungrazing Comets: Modeling of Their Mineralogical and Morphological Properties

Observations of sungrazing comets, all of which belong to the Kreutz family, provide the opportunity of studying the properties of dust in the comae and tails of the comets. On the basis of available information on cometary and interplanetary dust as well as observations of dust in the tails of sungrazers, we model dust in sungrazing comets as fluffy silicate aggregates of submicrometer sizes. To better interpret observational data, we numerically calculate the solar radiation pressure, the equilibrium temperature, and the sublimation and crystallization rates of silicate grains near the Sun. Our results show that the dust tails contain aggregates of submicrometer crystal grains, but not amorphous grains, since amorphous silicates mostly crystallize after release from the comets. The peak in the lightcurves of the dust comae observed either at 11.2 or 12.3 solar radii (R_⊙) seems to result from sublimation of fluffy aggregates consisting of crystalline or amorphous olivines, respectively. We attribute an additional enhancement in the lightcurves inside 7 R_⊙ to increasing out-flow of crystalline and amorphous pyroxenes composed fluffy aggregates. According to our model, the observed lightcurves indicate a high abundance of olivine and a low abundance of pyroxene in the comets, which may bear implications about the dynamical and thermal history of the sungrazers and their progenitor.     

Comet Grains: Their IR Emission and Their Relation to ISm Grains

Comets and the chondritic porous interplanetary dust particles (CP IDPs) that they shed in their comae are reservoirs of primitive solar nebula materials. The high porosity and fragility of cometary grains and CP IDPs, and anomalously high deuterium contents of highly fragile, pyroxene-rich Cluster IDPs imply these aggregate particles contain significant abundances of grains from the interstellar medium (ISM). IR spectra of comets (3–40 μm) reveal the presence of a warm (near-IR) featureless emission modeled by amorphous carbon grains. Broad andnarrow resonances near 10 and 20 microns are modeled by warm chondritic (50% Feand 50% Mg) amorphous silicates and cooler Mg-rich crystalline silicate minerals, respectively. Cometary amorphous silicates resonances are well matched by IRspectra of CP IDPs dominated by GEMS (0.1 μm silicate spherules) that are thought to be the interstellar Fe-bearing amorphous silicates produced in AGB stars. Acid-etched ultramicrotomed CP IDP samples, however, show that both the carbon phase (amorphous and aliphatic) and the Mg-rich amorphous silicate phase in GEMS are not optically absorbing. Rather, it is Fe and FeS nanoparticles embedded in the GEMS that makes the CP IDPs dark. Therefore, CP IDPs suggest significant processing has occurred in the ISM. ISM processing probably includes in He⁺ ion bombardment in supernovae shocks. Laboratory experiments show He⁺ ion bombardment amorphizes crystalline silicates, increases porosity, and reduces Fe into nanoparticles. Cometary crystalline silicate resonances are well matched by IR spectra of laboratory submicron Mg-rich olivine crystals and pyroxene crystals. Discovery of a Mg-pure olivine crystal in a Cluster IDP with isotopically anomalous oxygen indicates that a small fraction of crystalline silicates may have survived their journey from AGB stars through the ISM to the early solar nebula. The ISM does not have enough crystalline silicates (<5%), however, to account for the deduced abundance of crystalline silicates in comet dust. An insufficient source of ISMMg-rich crystals leads to the inference that most Mg-rich crystals in comets are primitive grains processed in the early solar nebula prior to their incorporation into comets. Mg-rich crystals may condense in the hot (～1450 K), inner zones of the early solar nebula and then travel large radial distances out to the comet-forming zone. On the other hand, Mg-rich silicate crystals may be ISM amorphous silicates annealed at ～1000 K and radially distributed out to the comet-forming zone or annealed in nebular shocks at ～5-10 AU. Determining the relative abundance of amorphous and crystalline silicatesin comets probes the relative contributions of ISM grains and primitive grains to small, icy bodies in the solar system. The life cycle of dust from its stardust origins through the ISM to its incorporation into comets is discussed.     

Demonstration of crystalline forsterite grain formation due to coalescence growth of Mg and SiO smoke particles

Abstract— Experimental studies of coalescence between Mg grains and SiO grains in smoke reveal the direct production of crystalline forsterite grains. The present results also show that different materials can be produced by grain‐grain collisions, which have been considered one of the models of grain formation in the interstellar medium. The fundamentals of coalescence growth in smoke, which have been developed in our series of experiments, are presented in this paper. Mg₂Si polyhedral grains were obtained in a Mg grain‐rich atmosphere. Mg₂SiO₄ polyhedral grains were obtained in a SiO grain‐rich atmosphere. The IR spectra of the resultant grains showed the characteristics of crystalline forsterite.     

Laboratory annealing experiments of refractory silicate grain analogs using differential scanning calorimetry

Abstract– Exothermic reactions during the annealing of laboratory synthesized amorphous magnesium‐bearing silicate particles used as grain analogs of cosmic dust were detected by differential scanning calorimetry (DSC) in air. With infrared spectroscopy and transmission electron microscopy, we show that cosmic dust could possibly undergo fusion to larger particles, with oxidation of magnesium silicide and crystallization of forsterite as exothermic reactions in the early solar system. The reactions begin at approximately 425, approximately 625, and approximately 1000 K, respectively, and the reaction energies (enthalpies) are at least 727, 4151, and 160.22 J g⁻¹, respectively. During the crystallization of forsterite particles, the spectral evolution of the 10 μm feature from amorphous to crystalline was observed to begin at lower temperature than the crystallization temperature of 1003 K. During spectral evolution at lower temperature, nucleation and/or the formation of nanocrystallites of forsterite at the surface of the grain analogs was observed.     

Crystalline silicates in comets: How did they form?

Two processes have been proposed to explain observations of crystalline silicate minerals in comets and in protostellar sources, both of which rely on the thermal annealing of amorphous grains. First, high temperatures generated by nebular shock processes can rapidly produce crystalline magnesium silicate grains and will simultaneously produce a population of crystalline iron silicates whose average grain size is ∼10-15% that of the magnesium silicate minerals. Second, exposure of amorphous silicate grains to hot nebular environments can produce crystalline magnesium silicates that might then be transported outward to regions of comet formation. At the higher temperatures required for annealing amorphous iron silicates to crystallinity the evaporative lifetime of the grains is much shorter than a single orbital period where such temperatures are found in the nebula. Thermal annealing is therefore unable to produce crystalline iron silicate grains for inclusion into comets unless such grains are very quickly transported away from the hot inner nebula. It follows that observation of pure crystalline magnesium silicate minerals in comets or protostars is a direct measure of the importance of simple thermal annealing of grains in the innermost regions of protostellar nebulae followed by dust and gas transport to the outer nebula. The presence of crystalline iron silicates would signal the action of transient processes such as shock heating that can produce crystalline iron, magnesium and mixed iron-magnesium silicate minerals. These different scenarios result in very different predictions for the organic content of protostellar systems.     

Low‐energy helium ion irradiation‐induced amorphization and chemical changes in olivine: Insights for silicate dust evolution in the interstellar medium

Abstract— We present the results of irradiation experiments aimed at understanding the structural and chemical evolution of silicate grains in the interstellar medium. A series of He+ irradiation experiments have been performed on ultra‐thin olivine, (Mg,Fe)₂SiO₄, samples having a high surface/volume (S/V) ratio, comparable to the expected S/V ratio of interstellar dust. The energies and fluences of the helium ions used in this study have been chosen to simulate the irradiation of interstellar dust grains in supernovae shock waves. The samples were mainly studied using analytical transmission electron microscopy. Our results show that olivine is amorphized by low‐energy ion irradiation. Changes in composition are also observed. In particular, irradiation leads to a decrease of the atomic ratios O/Si and Mg/Si as determined by x‐ray photoelectron spectroscopy and by x‐ray energy dispersive spectroscopy. This chemical evolution is due to the differential sputtering of atoms near the surfaces. We also observe a reduction process resulting in the formation of metallic iron. The use of very thin samples emphasizes the role of surface/volume ratio and thus the importance of the particle size in the irradiation‐induced effects. These results allow us to account qualitatively for the observed properties of interstellar grains in different environments, that is, at different stages of their evolution: chemical and structural evolution in the interstellar medium, from olivine to pyroxene‐type and from crystalline to amorphous silicates, porosity of cometary grains as well as the formation of metallic inclusions in silicates.     

Condensation processes in astrophysical environments: The composition and structure of cometary grains

Abstract— We review the results of our recent experimental studies of astrophysical dust analogs. We discuss the condensation of amorphous silicates from mixed metal vapors, including evidence that such condensates form with metastable eutectic compositions. We consider the spectral evolution of amorphous magnesium silicate condensates as a function of time and temperature. Magnesium silicate smokes anneal readily at temperatures of about 1000–1100 K. In contrast we find that iron silicates require much higher temperatures (?1300 K) to bring about similar changes on the same timescale (days to months). We first apply these results to infrared space observatory observations of crystalline magnesium silicate grains around high‐mass‐outflow asymptotic giant branch stars in order to demonstrate their general utility in a rather simple environment. Finally, we apply these experimental results to infrared observations of comets and protostars in order to derive some interesting conclusions regarding large‐scale nebular dynamics, the natural production of organic molecules in protostellar nebulae, and the use of crystalline magnesium silicates as a relative indicator of a comet's formation age.     

Low‐temperature crystallization of MgSiO3 glasses under electron irradiation: Possible implications for silicate dust evolution in circumstellar environments

Abstract— Synthetic MgSiO₃ glasses were irradiated at room temperature by 300 keV electrons in a transmission electron microscope (TEM). One of the samples had been previously irradiated by 50 keV He+ ions. Electron irradiation induces the nucleation and growth of randomly oriented nanometer‐sized crystallites. The crystallites first consist of MgO and subsequently of forsterite (Mg₂SiO₄). Both are seen to form within an amorphous SiO₂ matrix. The rate of crystallization of the samples has been monitored by conventional TEM imaging and electron diffraction. The sample that had been pre‐irradiated with He+ ions is found to transform faster than the as‐quenched glass. The crystallization of metastable MgSiO₃ glasses is explained by ionizing radiation‐induced elemental diffusion that allows the reorganization of matter into a more favourable thermodynamic state. These results show that ionizing radiation interactions could account for crystal formation as observed in infrared spectroscopy in some young stellar environments.     

The composition and size distribution of the dust in the coma of Comet Hale-Bopp

We discuss the composition and size distribution of the dust in the coma of Comet Hale-Bopp. We do this using a model fit for the infrared emission measured by the Infrared Space Observatory (ISO) and the measured degree of linear polarization of scattered light at various phase angles and wavelengths. The effects of particle shape on the modeled optical properties of the dust grains are taken into account. Both the short wavelength (7-44 μm) and the long wavelength (44-120 μm) infrared spectrum are fitted using the same dust parameters, as well as the degree of linear polarization at twelve different wavelengths in the optical to near-infrared domains. We constrain our fit by forcing the abundances of the major rock forming chemical elements to be equal to those observed in meteorites. The infrared spectrum at long wavelengths reveals that large grains are needed in order to fit the spectral slope. The size and shape distribution we employ allows us to estimate the sizes of the crystalline silicates. The ratios of the strength of various forsterite features show that the crystalline silicate grains in Hale-Bopp must be submicrometer-sized. On the basis of our analysis the presence of large crystalline silicate grains in the coma can be excluded. Because of this lack of large crystalline grains combined with the fact that we do need large amorphous grains to fit the emission spectrum at long wavelengths, we need only approximately 4% of crystalline silicates by mass (forsterite and enstatite) to reproduce the observed spectral features. After correcting for possible hidden crystalline material included in large amorphous grains, our best estimate of the total mass fraction of crystalline material is ∼7.5%, which is significantly lower than deduced in previous studies in which the typical derived crystallinity is ∼20-30%. The implications of this low abundance of crystalline material on the possible origin and evolution of the comet are discussed. We conclude that the crystallinity we observe in Hale-Bopp is consistent with the production of crystalline silicates in the inner Solar System by thermal annealing and subsequent radial mixing to the comet forming region (∼30 AU).     

Formaldehyde polymers in comets

The possibility that crystalline formaldehyde polymers are present in cometary dust is discussed. In common with most other parent molecules proposed for comets, (H₂CO) _n is difficult to detect, even if it is present in relatively high concentrations. The optical properties of these polymers in the visual and infrared regions are similar to those of silicate grains, and crystalline formaldehyde polymers provide no emission at 6 cm wavelength. The lifetime of gaseous H₂CO in the solar radiation field is too short, and the expected transitions in the microwave region would be too weak to be detected. However, the available data concerning the physical properties of comets indicate that polymerized formaldehyde cannot be ruled out as a major constituent of cometary material.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.     

The formation of Mg,Fe‐silicates by reactions between amorphous magnesiosilica smoke particles and metallic iron nanograins with implications for comet silicate origins

This thermal annealing experiment at 1000 K for up to 167 h used a physical mixture of vapor phase‐condensed magnesiosilica grains and metallic iron nanograins to test the hypothesis that a mixture of magnesiosilica grains and an Fe‐source would lead to the formation of ferromagnesiosilica grains. This exploratory study found that coagulation and thermal annealing of amorphous magnesiosilica and metallic grains yielded ferromagnesiosilica grains with the Fe/(Fe + Mg) ratios in interplanetary dust particles. Furthermore, decomposition of brucite present in the condensed magnesiosilica grains was the source for water and the cause of different iron oxidation states, and the formation of amorphous Fe³⁺‐ferrosilica, amorphous Fe³⁺‐Mg, Fe‐silicates, and magnesioferrite during thermal annealing. Fayalite and ferrosilite that formed from silica/FeO melts reacted with forsterite and enstatite to form Mg, Fe‐silicates. The presence of iron in different oxidation states in extraterrestrial materials almost certainly requires active asteroid‐like parent bodies. If so, the possible presence of trivalent Fe compounds in comet P/Halley suggests that Halley‐type comets are a mixture of preserved presolar and processed solar nebula dust. The results from this thermal annealing experiment further suggest that the Fe‐silicates detected in the impact‐induced ejecta from comet 9P/Temple 1 might be of secondary origin and related to the impact experiment or to processing in a regolith.     

Formaldehyde Polymers in Comets

The possibility that crystalline formaldehyde polymers are present in cometary dust is discussed. In common with most other parent molecules proposed for comets, (H₂CO)_n is difficult to detect, even if it is present in relatively high concentrations. The optical properties of these polymers in the visual and infrared regions are similar to those of silicate grains, and crystalline formaldehyde polymers provide no emission at 6 cm wavelength. The lifetime of gaseous H₂CO in the solar radiation field is too short, and the expected transitions in the microwave region would be too weak to be detected. However, the available data concerning the physical properties of comets indicate that polymerized formaldehyde cannot be ruled out as a major constituent of cometary material. This revised version was published online in July 2006 with corrections to the Cover Date.     

The composition of dust in Jupiter-family comets inferred from infrared spectroscopy

We review the composition of Jupiter-family comet (JFC) dust as inferred from infrared spectroscopy. We find that JFCs have silicate emission features with fluxes roughly 20-25% over the dust continuum (emission strength 1.20-1.25), similar to the weakest silicate features in Oort Cloud (OC) comets. We discuss the grain properties that alter the silicate emission feature (composition, size, and structure/shape), and emphasize that thermal emission from the comet nucleus can have significant influence on the derived silicate emission strength. Recent evidence suggests that grain porosity is the is different between JFCs and OC comets, but more observations and models of silicates in JFCs are needed to determine if a consistent set of grain parameters can explain their weak silicate emission features. Models of 8 m telescope and Spitzer Space Telescope observations have shown that JFCs have crystalline silicates with abundances similar to or less than those found in OC comets, although the crystalline silicate mineralogy of comets 9P/Tempel and C/1995 O1 (Hale-Bopp) differ from each other in Mg and Fe content. The heterogeneity of comet nuclei can also be assessed with mid-infrared spectroscopy, and we review the evidence for heterogeneous dust properties in the nucleus of comet 9P/Tempel. Models of dust formation, mixing in the solar nebula, and comet formation must be able to explain the observed range of Mg and Fe content and the heterogeneity of comet 9P/Tempel, although more work is needed in order to understand to what extent do comets 9P/Tempel and Hale-Bopp represent comets as a whole.     

Stability of amorphous circumstellar silicate grains

Within the framework of classical nucleation theory we have shown that Mg₂SiO₄ grains (radii of nearly 0.1 μm) which are likely candidates as condensation products in circumstellar shells around late-type stars must condense at about 750 K to remain amorphous. If the condensation temperature is about 1000 K the newly formed grains must be rather small to rest in the amorphous state during cooling. Submicron sized MgSiO₃grains are entire stable against crystallization for T_cond ≤ 1000 K.     

Amorphous Magnesiosilicate Smokes Annealed in Vacuum: The Evolution of Magnesium Silicates in Circumstellar and Cometary Dust

The mid-infrared spectral evolution of amorphous metastable eutectic magnesiosilica smokes, obtained by kinetically controlled gas-to-solid condensation of a Mg-SiO-O₂-H₂ vapor, proceeded in three distinct phases as a function of increasing time and temperature. This paper reports the mineralogical and chemical properties of these same samples. We found a previously unanticipated size dependence of the petrologic development of the initially amorphous magnesiosilica smokes that may also be at least partially responsible for the previously reported spectroscopic changes. Condensed grains less than approximately 20 nm in diameter remained amorphous throughout the thermal annealing experiment. Mineralogical changes occurred only after fusion of condensed magnesiosilica grains and chemical homogenization of large amorphous agglomerates and ring structures. Kinetically favored nucleation and growth produced the thermodynamically unstable nanocrystalline assemblage forsterite + tridymite. Further mineralogical development was stalled until continued fusing of agglomerates, rings, and some fraction of condensed grains had produced smooth amorphous magnesiosilica sheets of 42 and 20 wt% MgO. In rare sheets with more than ∼55 wt% MgO large forsterite crystals had grown, while enstatite had nucleated in low-MgO sheets still in the presence of forsterite and tridymite. The mineralogical evolution of the samples is critically dependent on the mass of the structural entities in the condensed sample and seems to be restricted to fused agglomerates and ring structures larger than about 20 nm in diameter and the sheet materials. We discuss the implications of our study for the interpretation of similar astrophysical dust analog studies and for astrophysical applications.     

Survivability of presolar oxygen isotopic signature of amorphous silicate dust in the protosolar disk

Oxygen isotope exchange experiments between tens of nanometer‐sized amorphous enstatite grains and water vapor were carried out under a condition of protoplanetary disk‐like low water vapor pressure in order to investigate the survivability of distinct oxygen isotope signatures of presolar silicate grains in the protosolar disk. Oxygen isotope exchange between amorphous enstatite and water vapor proceeded at 923–1003 K and 0.3 Pa of water vapor through diffusive isotope exchange in the amorphous structure. The rate of diffusive isotope exchange is given by D (m² s^–1) = (5.0 ± 0.2) × 10^–21 exp[–161.3 ± 1.7 (kJ mol^–1) R^–1 (1/T–1/1200)]. The activation energy for the diffusive isotope exchange for amorphous enstatite is the same as that for amorphous forsterite within the analytical uncertainties, but the isotope exchange rate is ~30 times slower in amorphous enstatite because of the difference in frequency factor of the reaction. The reaction kinetics indicates that 0.1–1 μm‐sized presolar amorphous silicate dust with enstatite and forsterite compositions would avoid oxygen isotope exchange with protosolar disk water vapor only if they were kept at temperatures below ~500–650 K within the lifetime of the disk gas.     

Influence of plasma on formation of crystalline Fe2SiO4 grains

The production of Fe₂SiO₄ (fayalite) crystalline grains was performed by two processes, namely, grain formation in a plasma field by evaporating a mixture powder of Fe and SiO and heat treatment of the product collected on the radio-frequency (RF) electrode side. Fe grains <20 nm in size covered with an amorphous SiO layer selectively formed Fe₂SiO₄ grains by heating at 800 °C. By heating at 600 °C, in addition to the formation of Fe₂SiO₄ crystal grains, the FeO phase appeared. The doping effect of excited oxygen in a plasma field into the Fe small grains may be the trigger on the formation of fayalite through the FeO phase formation. The present experimental result suggests that the probability of Fe₂SiO₄ grain formation in space is low.     

Grain Formation in Atmospheres of Cool Dwarfs

We have constructed a grid of model atmospheres for cool dwarf stars and brown dwarfs with T_eff ≤ 3000 K that includes (i) an equation of state which accounts for over 600 gas phase species and 1000 liquids and solids, and (ii) the opacities of corundum (Al₂O₃), iron, enstatite (MgSiO₃) and forsterite (Mg₂SiO₄), as well as amorphous carbon and SiC. We confirm earlier findings of Tsuji, Ohnaka & Aoki (1996a) that grains are abundant in the outer photospheric layers of red and brown dwarfs with spectral type later than M8. We identify high temperature condensates including perovskite (CaTiO₃) that depletes the photospheres of important absorbers including TiO, and we confirm the disappearance of TiO bands in the observed spectra of cool dwarfs. This revised version was published online in September 2006 with corrections to the Cover Date.